Helium diffusion in mantle minerals is crucial for understanding mantle structure and the dynamic processes of Earth's degassing.In this paper,we report helium incorporation and the mechanism of its diffusion in perfect crystals of quartz and coesite.The diffusion pathways,activation energies(Ea),and frequency factors of helium under ambient and high pressure conditions were calculated using Density Functional Theory(DFT)and the climbing image nudged elastic band(CI-NEB)method.The calculated diffusive coefficients of He in the quartz in different orientations are:D[100]=1.24×10^(−6)exp.(−26.83 kJ/mol/RT)m^(2)/s D[010]=1.11×10^(−6)exp.(−31.60 kJ/mol/RT)m^(2)/s.and in the coesite:D[100]=3.00×10^(−7)exp.(−33.79 kJ/mol/RT)m^(2)/s D[001]=2.21×10^(−6)exp.(−18.33 kJ/mol/RT)m^(2)/s.The calculated results indicate that diffusivity of helium is anisotropic in both quartz and coesite and that the degree of anisotropy is much more pronounced in coesite.Helium diffusion behavior in coesite under high pressures was investigated.The activation energies increased with pressure:Ea[100]increased from 33.79 kJ/mol to 58.36 kJ/mol,and Ea[001]increased from 18.33 kJ/mol to 48.87 kJ/mol as pressure increased from0 GPa to 12 GPa.Our calculations showed that helium is not be quantitatively retained in silica at typical surface temperatures on Earth,which is consistent with the findings from previous studies.These results have implications for discussion of the Earth's mantle evolution and for recognition thermal histories of ultra-high pressure(UHP)metamorphic terranes.
A series of coesite,coexisting with or without a liquid phase,was synthesized in the nominal system SiO2-H2O at800-1450℃and 5 GPa.Micro-Raman spectroscopy was used to identity the crystalline phase,electron microprobe and LA-ICP-MS were employed to quantity some major and trace elements,and unpolarized FTIR spectroscopy was applied to probe the different types of hydrogen defects,explore water-incorporation mechanisms and quantify water contents.Trace amounts of A1 and B were detected in the coesite.Combining our results with the results in the literatures,we have found no positive correlation between the Al contents and the"Al"-based hydrogen concentrations,suggesting that previously proposed hydrogen-incorporation mechanism H^++Al^3+■Si^4+does not function in coesite.In contrast,we have confirmed the positive correlation between the B contents and the B-based hydrogen concentrations.The hydrogen-incorporation mechanism H^++B3^+■Si^4+readily takes place in coesite at different P-T conditions,and significantly increases the water content at both liquid-saturated and liquid-undersaturated conditions.For the SiO2-H2O system,we have found that type-Ⅰhydrogarnet substitution plays a dictating role in incorporating water into coesite at liquid-saturated condition,type-II hydrogarnet substitution contributes significantly at nearly dry condition,and both operate at conditions in between.The water solubility of coesite,as dictated by the type-Ⅰhydrogarnet substitution,positively correlates with both P and T,cH2O=-105(30)+5.2(32)×P+0.112(26)×T,with cH2O in wt ppm,P in GPa and T in℃.Due to its low water solubility and small fraction in subducted slabs,coesite may contribute insignificantly to the vertical water transport in subduction zones.Furthermore,the water solubility of any coesite in exhuming ultra-high pressure metamorphic rocks should be virtually zero as coesite becomes metastable.With an adequately fast waterdiffusion rate,this metastable coesite should be completely dry,which may have been the ke
Wei YanYanyao ZhangYunlu MaMingyue HeLifei ZhangWeidong SunChristina Yan WangXi Liu
Trace element partitioning between coesite and hydrous silicate melt has been investigated at 5 GPa and 1500-1750℃.High-P experiments successfully produced large coesite crystals in equilibrium with large silicate melt pools(plus kyanite and corundum crystals in some cases).Scanning electron microscopy and micro-Raman spectroscopy were employed to characterize the phases and the textures.Wavelength-dispersive electron microprobe analyses were performed to quantify conventional major elements,and laser ablation-inductively coupled plasma-mass spectrometry analyses were successfully conducted to quantify trace elements.Eventually,high-P partition coefficients were obtained for 33 elements.In general coesite is a very pure phase.With a few possible exceptions like Sc,Ti,and V,nearly all other trace elements are incompatible in coesite.Moreover,the partitioning behaviors of nearly all trace elements except some 4+cations cannot be readily described by the lattice strain model,presumably implying a minor role for the cation size in the trace-element partitioning.Combining our experimental results with the results in the literature,some T and P effects on the element partitioning behavior have been observed:T seemingly has different effects on different trace elements,but P might negatively correlate with the partition coefficients in all cases.Due to its large modal fraction in some subducted materials such as the continental crustal material,coesite might play an important role in the distributions of some trace elements,Ti for example.
The sediments,including calcareous,siliciclastic and volcanoclastic,usually occupy>90%in volume of an accretionary complex and thus,if involved in subduction zones,their maximum return depths(i.e.,peak pressures)are fundamental to unravel the geodynamic processes during the convergence of plates[1].As a unique example of accreted complex returned from sub-arc depths(>90 km)worldwide.
Ultrahigh-pressure (UHP)metamorphism plays important roles in continental dynamics.Understanding of this process has been enhanced by the discovery of coesite and micro-diamond from supracrustal rocks [1].Such UHP mineral inclusions provide unequivocal evidence that the least dense part of the lithosphere can be buried to 100-150km or more,and then returned to the surface.Coesite,an ultrahigh-pressure polymorph of SiO2stable above 2.7GPa at metamorphic temperatures,is one of the most important index minerals for UHP metamomhism [1,2].